Catalysis and tunnelling in the unimolecular decay of Criegee intermediates

Burd, Timothy; Xiao, Shan; Clary, David C.

doi:10.1039/c8cp05021j

Cited by 11 publications

(27 citation statements)

References 67 publications

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“…We first discuss here the one-dimensional approach, which has been applied to various reactions, including H abstractions, 24,32,38 H exchange, 39 and unimolecular H transfers. 40,41 In Section 4, we shall explain the limitation of this method and suggest possible solutions.…”

Section: D Sctstmentioning

confidence: 99%

New Developments in Semiclassical Transition-State Theory

2019

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This Feature Article describes some recent developments and applications of the Semiclassical Transition State Theory (SCTST) for treating quantum tunnelling in chemical reactions. A reduced dimensional form of the SCTST is discussed and is shown to be particularly efficient as the required number of electronic structure calculations is reduced to an absolute minimum. We also describe how an alternative formulation of SCTST, called SCTST-θ, has advantages in allowing for straightforward applications of the SCTST for any form of the potential expansion at the transition state. We also illustrate the power of SCTST in applications to more complex systems. We show how polyatomic modes such as internal rotations and torsions can be treated efficiently in SCTST calculations. We also describe some applications of the method to hydrogen atom tunneling in unimolecular reactions including the degradation of chemical nerve agents and the decay of the atmospherically important Criegee intermediates.

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Section: D Sctstmentioning

confidence: 99%

New Developments in Semiclassical Transition-State Theory

2019

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“…62 In the DT correction proposed by Wagner et al 62 eqn (3) is replaced by a piece-wise continuous asymmetric Eckart barrier model. It improves the results at temperatures typically lower than 500 K. 21,36,[39][40][41]54 The additional computational cost of constructing the DT barrier is only the reverse barrier height.…”

Section: One-dimensional Semiclassical Transition State Theorymentioning

confidence: 93%

“…In the current study, adapting the reduced dimensionality framework, [63][64][65] we propose a method that is somewhat in between SS-HR and MS-T. Before we going into details of this method, it is helpful to discuss the locality of a vibrational mode. 41,66 For a particular vibrational mode, Q, it is given by…”

Section: Approximated Hindered Rotor Treatmentmentioning

confidence: 99%

“…In practice, the numerical computations of these anharmonic constants can introduce unnecessary error in a FD calculation. In the current study, we employ the one-dimensional (1D) SCTST, 21,36,[39][40][41] which is a much less expensive and yet sufficiently accurate approximation to the FD SCTST. We have used the 1D SCTST in a combined experimental and theoretical study of a pericyclic H-transfer reaction of sarin, 21 similar to the title reactions, and found excellent agreement between the two.…”

Section: Introductionmentioning

confidence: 99%

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Calculations on the unimolecular decomposition of the nerve agent VX

Xiao

Sambrook

Clary

2020

Phys. Chem. Chem. Phys.

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“…One such theory is Semiclassical Transition State Theory (SCTST), as developed originally by Miller et al [10]. This has previously been applied and tested on a variety of polyatomic reactions [11][12][13][14]. Applying the theory in reduceddimensions allows for even greater efficiency, and has been shown to be nearly as accurate as the full-dimensional treatment in many cases, despite the significant computational saving [15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Tunnelling in cyclocarbenes: An application of Semiclassical Transition State Theory in reduced dimensions

Burd¹,

Xiao²,

Clary³

2019

Chemical Physics Letters

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Methods to calculate rates of chemical reactions ab initio, in reduced dimensions, using Semiclassical Transition State Theory have recently been formulated. Here we further develop its application to unimolecular reactions where the choice of active degrees of freedom is not clear a priori. We describe in more detail a procedure to determine which degrees of freedom must be accounted for explicitly in the reduced dimensionality framework, and illustrate its success on a hydrogen transfer reaction of a cyclocarbene species.

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Catalysis and tunnelling in the unimolecular decay of Criegee intermediates

Abstract: Semi-classical Transition State theory can be applied to catalysed atmospheric reactions, but reaction mode anharmonicity must be treated carefully.

Cited by 11 publications

References 67 publications

New Developments in Semiclassical Transition-State Theory

New Developments in Semiclassical Transition-State Theory

Calculations on the unimolecular decomposition of the nerve agent VX

Tunnelling in cyclocarbenes: An application of Semiclassical Transition State Theory in reduced dimensions

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